Process of hydrocarbon treatment and regeneration



Jan. 17, 1950 W. S. BONNELL PROCESS OF HYDROCARBON TREATMENT AND REGENERATION Filed Jan. 5, 1.948

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WILLIAM 0. 11011102101 Patented Jan. 17, 1950 PROCESS OF HYDROCARBON TREATMENT AND REGENERATION William S. Bonnell, Port Arthur, Texl, assignor to Gulf Oil Corporation, Pittsburgh, Pa a corporation of Pennsylvania Application January 5, 1948, Serial No. 534

4 Claims. 1

This invention relates to improved process of the type wherein a catalyst, adsorbent or the like, in pellet form is contacted with a hydrocarbon vapor until it is at least partially deactivated following regeneration to remove carbon by combustion.

It is conventional procedure in catalytic processes such as the cracking of petroleum and petroleum fractions to utilize a catalyst in the form of pellets and to contact the pellets alternately with petroleum vapors to be catalytically con- Verted and with a regenerating gas to remove carbon from the catalyst pellets by combustion. The regeneration is accomplished by introducing the pellets into the top of a kiln through which they flow downwardly as a moving bed while in contact with air or oxygen containing gas which serves to burn off the deposited carbon. The regenerated pellets then are returned to the cracking reactor for reuse. This combustion releases considerable heat and the rate of burning must be controlled. Thus, the amount of air or oxygen delivered to the individual zones of the kiln can be varied and each zone of the kiln is equipped with cooling coils to remove the heat released by the combustion. Excessive temperature damages the kiln internals and rapidly deactivates the cat-. alyst. Thus, it is desirable to limit the maximum regeneration temperature to about 1150 F.

However, even with the above means of controlling the rate of burning, when operating with the the two walls of commercial kilns parallel to the nance of even temperatures. 7 nature of the carbon burning reaction and the 2 cooling coil tubes and air distributors and the catalyst adjacentto these walls operate at tam-- peratures in excess of 1200 F. because of insufficient cooling. The catalyst within one foot of these two walls is from 100 to 400 F. hotter in the upper zones than the catalyst in the main section of the kiln. The flue gas outlet distributors pass through these two walls and tend to lose lack of cooling, the excessive temperature condition rapidly pyramids, the lack of sufficient cooling resulting in high temperatures which speed up the rate of burning and cause still higher temperatures.

It is known that catalystsand especially those of the cracking type become deactivated during use. Excessive temperature will rapidly deactivate a catalyst and the rate at which the deactivation takes place is a function of the time of heating and the temperature. The harmful effect of excessive temperatures on the activity of a natural silica-alumina catalyst is shown in Table I. In this case the catalyst samples were heated 35 in the presence of air alone.

Table I 1 3% T 'i d T t d T t d ea c rea e tea e rea e Description of Treatment Untreated 8 Hm at 4 Hrs. at 8 Hm at 8 Hrs. at 1100 F 1300 F 1300 F. 1500 F.

Inspection:

Activity Index-- CAT-A Method:

Gasoline, Per Cent by Vol. LB- 41. 6 37.8 37.0 35. 4 9. 29 Gas, Per Cent by Wt 5.79 4. 55 3. l 3. 0. 61 Sp. Gravity. 1... 1.45 1. 39 1. 29 1.26 1. 07 Coke, Per Cent by Wt 3.80 3. 51 2. l4 2. 72 0.56 Ignition Loss, Per Cent by Wt.: Filtrol ethod. 6. 3. 52 2. 95 2.38 l. 39 Attrition Loss, Per Cent by Wt 25. 0 13. 15. 7 12. 5 15. 5 Hardness Index, Per Cent by Wt" 76. 0 86.35 84. 3 87. 5 84. 4 Apparent Density, (L/Cc.-. 0.68 0. 0. 72 0.72 1.06 Sieve Analysis,Per Cent by'Wt;

Socony-Vacuum Method- O 3 none none none

It has been further observed that the rate of deactivation is even more severe when the catalyst is overheated in the presence of steam. In

Table II the activities of samples of the same natural silica-alumina catalyst are shown after heating at the temperatures indicated in an atmosphere of steam.

In commercial operation some. steamis present: in the regeneration kiln due to moisture inithe'; air, presence of combined: hydrogen: in the coke: deposit on the catalyst, process steam-adsorbed? by the catalyst in the. reactor, and burning; of natural' gas in an airline burnerto-preheat theair forrregeneration; I have made measurements? in the regenerating kilns of commercial. cracking units in which catalyst temperatures-as-high as 1500 F. were obtained-in the area adjacent to the two hotwalls, even though the main-portion' of the catalystwas'contrcllod for a maxi mum temperature of 1150 F. apparent that the. hot wall condition: results. in excessive temperatures, which are a major factor inloss of catalyst activity.

Activity. index as used herein is the. cracking activity as determined by. Catalyst activitytestsA (Catalogue A) publishedby the Catalytic Development C.orp..,, Houdry Process Corp. and Socony-Vacuum. Oil Co.

This invention has for its object to provide improved catalytic, adsorption, etc., process. ther object is to..provide improvedhydrocarbon cracking process. whereby the. foregoing difliculties can be overcome. Another object isto provide procedure. whereby catalyst pellets can It. is. therefore be used to control temperatures in a regenerat ing kiln. A; still further object is to provide a process for the continuous catalytic conversion of pear hereinafter.

These and other objects are accomplished by my invention whichincludes. the. step of introducing a contact agent such as an adsorbent or catalys u in pellet form, which is substantially paratus provided with means for delivering catalyst pellets which are substantially free of carbon, such as regenerated catalyst pellets, to overheating sections of the regenerating" kiln;

Figure 2 is a fragmentary enlarged View of the top portion of the regenerating kiln shown in Figure 1;

Figure 3 is a horizontal section of the kiln takenon line 33' of Figure 2; and

Figure 4 is a comparison of temperature readings made at appropriate points near the kiln wallsof a commercial cracking unit, similar to that shown in Figs. 1-3, when operating with and without recirculation of regenerated catalyst.

Referring to Figures 1, 2 and 3, numeral 5 designates a continuous reactor for contacting hydrocarbon vapors or mixed hydrocarbon liquidvapors with cracking: catalyst pellets such as silica-alumina pellets,.which are preferably about the size ofai small pea. The catalyst pellets are continuously introduced into-the reactor 6 from hopper 8 by way-of delivery conduit. l0. Numeral.

l2 designates a conduit for introducing thezhydrocarbon vapors into. the reactorwhile conduit I l is providedfor removing cracked hydrocarbon vapors from thereactor; With this arrangementthe flow is countercurrent. It is also'common practice to operate with concurrent flow; i. e., the hydrocarbon vapors are introduced through conduit' l4 and removed through conduit l2. After passage through the reactor the-catalyst pellets are steamed to remove hydrocarbon vapors by.

steam introduced through conduit I6. After the steaming operation the catalyst pellets flow through delivery tube 20 into elevator mechanism 22 andare delivered thence'into kiln as by way of tube 26; Thiskiln is of conventional construction, havinga rectangular cross section and con sistingof'anumberofzones equipped with means for distributingair and collecting flue gas in each zone. Also each zone contains cooling coils for removing heat released by combustion. The catalyst pellets are continuously introduced from kiln. hopper 28.. into the kiln z i'where the? carbon deposited thereon is burned off at elevated'temperaturewith air introduced into the sections of the kiln through conduits 30 by blower 34. Com.- bustion or flue gasespass from the sections of. the kilnthrough oonduits32 and these gases are delivered to the elutriator andstackby way of conduit 33.. This combustioniscondueted in known manner to remove most of the carbon deposited on the catalyst pellets. The catalyst pellets fiow downward by gravity through the sections of the kiln and thence through conduit 36 into the intake of elevator-3&which elevates the regenerated pelfree of carbon, into that portion of the kiln which tends to become overheated. It has been of combustible material thereon, result in. a re-- duction-in temperature inthat portion of the re:

generator.

In the following examples and.v description. I

have given several of thepreferred: embodiments of my invention, but it. is. to beunderstoodthat. they are set forth for the purpose of illustration and not in'limitation thereof.

Referring to the drawings? continuous hydrocarbon catalytic cracking ap- V drawn: catalyst flows through conduit 44 into lets and returns them by way of tube 4!) to the reactor hopper" 8- for' reuse.

It is customary in such a catalytic process to continuously: remove undersized particles by elutriation. This is accomplished in the apparatus illustrated by drawing 01f part of the regen eratedj catalyst fromthe draw ofi boot 42 positioned'at the discharge of elevator 38. This withelutri'ator 46 positioned in kiln flue 48. In the elutriator the catalyst granules are continuously brought-into contact with a rapidly moving stream offi'ue gas. introduced through conduit 33. The

' stream of gas-carries or sweeps with it any small or. undersized particles of catalyst which particles I r are separated iii-cyclone in known manner. Figure'l'isadiagrammatical elevation of a"- The'cataiyst pell-ets then pass from the elutriator through conduit 54 and valve 52 back into the main stream of catalyst pellets in conduit 36 as indicated. r

Numeral 56 designates a distributing pot into which catalyst pellets flow from conduit 58 at a rate controlled by valve 60. Numerals B2 to B8 and in to TB designate conduits for supplying catalyst from pot 55 to sections of the kiln 24 which becomed overheated. For convenience it will be assumed that the east and west walls become overheated for the reasons pointed out above. Conduits 62 to 68 are therefore shown as delivering catalyst to the east wall and conduits l0, l2, l4 and 16 as delivering catalyst to the west wall. Numeral l8 designates a plurality of short or truncated conduits integral with the plate 80 of kiln hopper 2B. These conduits are positioned as indicated so as to deliver catalyst pellets from hopper 28 into the kiln 24 in an evenly distributed manner. The lower ends of conduits 62. 6'4, 66 and 68 are positioned so that they discharge catalyst into the area between conduits l8 and the east wall of kiln 24. Corresponding conduits Ill, 12, 14 and 16 (see Fig. 3) are positioned so as to introduce catalyst from distributing hopper 56 against the west wall of the kiln. All of these conduits 62-68 and Ill to 16 are provided with suitable flow controlling devices such as orifices 84.

Referring particularly to Figs. 2 and 3, it will be noted that each conduit 62 to 16 is positioned between a hot wall and a downcomer 18. The catalyst flows in a pile from each downcomer as indicated by the dotted line 86. Therefore the catalyst level at the walls of the kiln is lower than at the downcomers and the catalyst profile along the wall varies in a regular pattern, being highest "at the downcomer centerline and lowest midway between the downcomers. Because of this char' acteristic flow pattern I have been able to distribute the regenerated catalyst evenly across the wall by using a distributor pipe for each downcomer along the face of the hot walls. Uniformity of the temperature across the hot wall is obtained by this even distribution of regenerated catalyst. In operating the apparatus illustrated in Figs. 1, 2 and 3, hydrocarbon oil vapors are introduced into the reactor 6 through conduit I2 and catalyst pellets are introduced into the reactor from hopper 8 byway of conduit Ill. Cracked hydrocarbon vapors are removed through conduit H, and steam is introduced through conduit IS. The catalyst pellets pass downwardly by gravit as a moving bed through the reactor 6 and when they reach the lower portion thereof they are stripped of hydrocarbons by the stripping steam. The catalyst pellets then pass by gravity through conduit 28 into the base of elevatorZZ, are elevated and pass from the top of the elevator through conduit 26 into the kiln hopper '28 at the top of kiln 24. This catalyst then passes through the down-comer conduits 18 into the kiln where they are contacted with air at elevated temperature so as to burn off the deposited carbon. The catalyst pellets pass as a moving bed downwardly through the several zones of the kiln and finally pass into the conduit 36 at the base of the kiln,

thence into elevator 38, conduit 40 and back to the reactor hopper 8. Part of the regenerated catalyst is withdrawn through boot 42, conduit 44, and is separated from fines in elutriator 46 and is returned to the base of elevator 38 by way of con.- duits 54 and 36. 1

' Part of the catalyst from elutriator feed conduit 44 passes through conduit 58 and valve 50 into the distributor pct 56. This catalyst then flows through conduits 62-66 and 'l0|6 and is 6 distrlbutedagainst the east and west walls of the kiln as shown in detail in Figures 2 and 3. Pot 5B is run full of catalyst to evenly fill the distributing conduits which also run full and thus prevent leakage of flue gases through this part of the system. Orifices '84 in these conduits. are of such size as to permit the flow of the desired amount of catalyst to control the temperature in the overheating zones. This regenerated catalyst then flow-s downwardly by gravity against the east and west walls of the kiln and finally flows into conduit 36 with the rest of the catalyst which has been regenerated;

Example A commercial unit similar to that illustrated in Figures 1 to 3 utilizing a natural silica-alumina catalyst to crack heavy gas oil was operated with a total of nine tons per hour of regenerated catalyst circulated to the east and west walls of the regenerator kiln through four conduits positioned near each of these walls. The regenerated catalyst was distributed evenly against the east and west walls of the kiln in order to eliminate a hot wall condition which would otherwise have existed due to insuificient cooling as previously explained. The temperatures of these two walls at two of the zones near the top of the kiln before circulating the regenerated catalyst thereto (solid lines) and after circulating regenerated catalyst (dotted lines) are shown in Figure 4. It will be noted that the temperature of the hot east and west walls was reduced from about 1100 to 1400 F. to 700 to 800 F. and that the temperature was made more uniform as evidenced by the relative lack of peaks in the dotted curves. The uniformity of the temperatures across the walls is due to good distribution of. the regenerated catalyst along the wall, as is explained in detail above. Since the regenerated catalyst contained only about 0.1 per cent by weight of carbon as compared with about 2 per cent by weight for the catalyst undergoing regeneration it is apparent that the reduction in temperature resulted from a decrease in the amount of carbon burned in these areas. This system has been in continuous operation and has permitted maintaining the system catalyst above 30 activity index with less: than 3 T/D fresh catalyst makeup. Prior to installation of this system the catalyst activity could not be maintained above 25 with more than 3 T/D fresh catalyst makeup. The temperature surveys and catalyst activity experience to date indicate that it may be possible to reduce the regenerated catalyst recirculation several tons per hour without encountering excessive temperatures and catalyst deactivation at the walls. In this example the total circulation of catalyst in the system was tons/hour and a total of 3500 lbs./

hour of carbon was being burned in the kiln.

While I have found it convenient to describe my invention in connection with a hydrocarbon cracking process utilizing a silica-alumina cracking catalyst it is to be understood that it is ap plicable to any regenerating process in which a becomes deactivated by heating to the excessive temperatures which are frequently encountered during such regeneration. ,Thus the process of my invention is applicable to other cracking catalysts such as silica-magnesia, 'zirconia-silica; titania-silica' "and alumina-zirconia-silica cataasses e lysts;. It: is also applicable, to; easilyreduciblee meal oxideslzsuch-as; oxides of; n fil; ob l d: iron and to: difficultly reducible oxides such as: oxides; of chromium, molybdenum, and tungsten. all of which. are: generally used onporous carrierssuch; as alumina and/or silica. These catalystsmay-be used iorhydrogenation, dehydrogenation, desulfurizatiom aromatization; etc: -My invention also can be employed in the regeneration. of contact. agents used for non-catalytic purposes such as; adsorption. For instance my invention canibe utilized-.to-regenerate fullersearth or-buxite pellets after they have beenusedtoidecolorize lubricating oils.

Many catalytic operations are conducted in reactors-of thefixed bed type; 1.16; the catalyst is maintained: in a stationary position during the period of= time. used for; conversion of. the; reactants. At" intervals, thercatalyst: is removed. from the reactor and? regenerated by circulation through a kiln similar. to; that previously described; It-isto be understood: that" my invention can be. used to. regenerate catalysts: which have become deactivated irrsuch-fiXedbed-processes.

While I'preferxto circulate regeneratedflcatalyst to the areas which; overheat;. it; is' obvious: that freshcatalyst: which: must; be introduced into the system to replace. catalyst? lost. by attrition orv for any other purpose can also, be used to replace. part: or all: of theregenerated1 catalyst; Also the. regenerated; catalyst; distributing conduits can. be" varied? in. size, number and location so as to deliverthe necessary amount of regenerated: catalyst with the proper distribution to any location: which tends; to: overheat.

It is known. to: introduce: elutriated, and regeneeratedi catalyst into. thecenter of. the kiln; However'this isdone merelyas a convenient: method of returning the catalyst; to the system and is. not. for the purpose of. controlling; overheating zones. Because of the conventional cooling coils the center ofi'the. kiln does'wnot' overheat;

Itisevident from the foregoing that my in.- vention providesa positive'meth'od for controlling the temperature of local areas in a regenerating kiln of the moving bed. type. It; also follows that my invention greatly prolongs the useful lift of' a catalyst by avoiding overheating and consequent dreactivation.v The installation cost islow since. only piping is; required: and. the: con trol of the. flow of regenerated catalyst. can be varied easily by changing orifices which can be done while the system. is. in operation. Resinculatingthe regenerated catalyst through the kiln does not decreasecarbon: burning capacity. Actually, with the hot wall condition controlled, the carbon-load can-be increased.

What I claim is:

1. In the process ofcracking a hydrocarbon oil by contacting vapors thereof with heated catalyst pellets moving downwardly by gravity through a reactor followed byregenera-tion of the catalyst pellets by introducing-them into the top of an approximately vertical regenerator through which they pass downwardly-by gravity while at elevated temperature and"v while in contact with oxygen containing gas, the improvement which comprises introducing previously": regenerated catalyst pellets into the regenerat'or against the top: of a. wall. of theregenerator which during regeneration becomes overheated whereby the regenerated catalyst. pellets; flowdownwardly along the. wall of the. regeneratorwhich tends to=becomeoverheated and: due tnzthelack oizcombustible-mater-ialathereon cause. a reduction in the temperature of the regenerator wall.

2-. In theprocess. of cracking. a hydrocarbon-oil by contacting; vaporsthereot with heatedcatalyst.

I pellets moving. downwardly by. gravity through a reactor followed by regeneration of. thecatalyst. pellets by introducing. them; into the top of. an approximately vertical regenerator through which. they pass-downwardly by gravity while atelevated temperature.- and while in contact with oxygen.

of; said regenerator wall.

3. In the process. of. cracking a hydrocarbon oil by contacting vapors; thereof. with heatedsilica-aluminacracking catalyst. pellets moving downwardly by gravity through-areactor followed by regeneration ofthe; catalyst. pellets. by introducing' them into'the top; of an approximately vertical regenerator through which they pass downwardly by gravity whileat elevatedtemperature-and while in; contact with oxygen containing gas, the improvementwhich comprises intro.- ducing previously regenerated catalyst pellets into the regenerator-against.thetopof a wallof, the regenerator which during regeneration becomes overheated whereby the-regenerated catalyst pel- 1 l'etsflow downwardly-along;the-wall of theregeneratorwhich tends;tobecomeoverheated and: due to the lack of combustible-material thereon-causeae: reductionin the-temperature Y of-v the regenerator wall.

4; The. process of. regenerating, catalyst. pellets which are contaminated with carbon as a result of use in a hydrocarbon cracking process which comprises allowing; said contaminated; catalyst pelletstodescendby gravity-through a regenerating chamber in the presence of. oxygen at com:- bust-ion temperature.- and simultaneously introducing into saidregenerating. chamber in contact with at least one of the interior wallsthereof, a second portion of catalyst which contains a substantially lesser quantity of carbon than the catalyst to. be-regeneratedwherebythis catalyst of lesser. carbon. content flows downwardly along the interior wall andv prevents the combustion temperature near the wall of the regenerating chamber from reaching a degree suflicient to overheat the wall, and preventing intermingling of the second portion of catalyst which is introduced against theinterior wall: with the catalyst tobe regenerated to an extent sumcient to maintain a lower temperature along the wall than in thecatalysti; to berregenerated.

WILLIAM. S; BONNELL.

REFERENCES; CITED The following references are of record in the file of" this. patent:

UNITED STATES," PATENTS Number Name Date 2,395,106 Day et al Feb. 19, I946 2,416,214 Payne. Feb. 18, 1947 2,433,813. Lechthaler. et a1. .July 8, 119.47 234583.50; Crowley. Jr., Jan. 4, 1949 

1. IN THE PROCESS OF CRACKING A HYDROCARBON OIL BY CONTACTING VAPORS THEREOF WITH HEATED CATALYST PELLETS MOVING DOWNWARDLY BY GRAVITY THROUGH A REACTOR FOLLOWED BY REGENERATION OF THE CATALYST PELLETS BY INTRODUCING THEM INTO THE TOP OF AN APPROXIMATELY VERTICAL REGENERATOR THROUGH WHICH THEY PASS DOWNWARDLY BY GRAVITY WHILE AT ELEVATED TEMPERATURE AND WHILE IN CONTACT WITH OXYGEN CONTAINING GAS, THE IMPROVEMENT WHICH COMPRISES INTRODUCING PREVIOUSLY REGENERATED CATALYST PELLETS INTO A REGENERATOR AGAINST THE TOP OF A WALL OF THE REGENERATOR WHICH DURING REGENERATION BECOMES OVERHEATED WHEREBY THE REGENERATED CATALYST PELLETS FLOW DOWNWARDLY ALONG THE WALL OF THE REGENERATOR WHICH TENDS TO BECOME OVERHEATED AND DUE TO THE LACK OF COMBUSTIBLE MATERIAL THEREON CAUSE A REDUCTION IN THE TEMPERATURE OF THE REGENERATOR WILL. 